Correlating Cu dopant concentration, optoelectronic properties, and photocatalytic activity of ZnO nanostructures: experimental and theoretical insights.

The photocatalytic activity of photocatalysts can be enhanced by cation doping, and the dopant concentration plays a key role in achieving high efficiency. This study explores the impact of copper (Cu) doping at concentrations ranging from 0% to 10% on the microstructural, optical, electronic, and photocatalytic properties of zinc oxide (ZnO) nanostructures. The X-ray diffraction analysis shows a non-linear alteration in the lattice parameters with increasing the Cu content and the formation of CuO as a secondary phase at the Cu concentration of >3%. Density functional theory (DFT) calculations provide insights into the change in the electronic structures of ZnO induced by Cu doping, leading to the formation of localized d electronic levels above the valence band maximum. The modulation of the electronic structure of ZnO by Cu doping facilitates the visible light absorption via O 2p → Cu 3d and Cu 3d → Zn 2p transitions. Photoluminescence spectroscopy reveals a quenching of the defect-related emission peak at approximately 570 nm for all Cu-doped ZnO nanostructures, indicating a reduction in the structural and other defects. The photocatalytic activity tests confirm that the ZnO nanostructures doped with 3% Cu exhibit the highest efficiency compared to other samples due to the suitable band-edge position and visible light absorption.